Membrane evaluation for the treatment of acidic clear filtrate

The total effluent load of a paper mill can be significantly decreased by recycling of purified clear filtrate (CF) back to paper-making process. The CF treated with membranes can be reused, for instance, as wire section shower water and in the dilution of chemicals. The main requirements for a membrane in CF treatment are high filtration capacity, high retention of turbidity and low fouling tendency. Previous studies have shown that the regenerated cellulose (RC) ultrafiltration (UF) membrane C30F (current trade name UC030T) is especially suitable for the treatment of paper mill process waters. Every paper-making process is, however, different. Thus, filtration experiments are required in order to find the most optimal membrane for the treatment of a certain process water. In this study the best membrane for the treatment of acidic clear filtrate (ACF) was searched. The performance of the C30F membrane was compared with five UF and three microfiltration (MF) membranes. The results revealed that in addition to the C30F membrane, also some other membranes produced high filtration capacity with ACF (approximately 200 L/(m²h bar)). All the tested membranes also retained over 90% of turbidity. The extremely hydrophilic C30F membrane had, however, lower fouling tendency compared to the other tested membranes. Therefore, it was concluded that the C30F membranes were the best possible membrane for the ACF treatment.     

Recast Nafion‐117 thin film from water solution

Perfluorosulfonated ionomer (PFSI) dispersions in various solvents, usually mixtures of organic compounds and water, were used to prepare the membrane‐electrode system in polymer electrolyte membrane fuel cells (PEMFC), the aim being to increase performance by improving the triple contact of graphite (electron conducting material), Pt (hydrogen dissociation catalyst) and ionomeric membrane (proton conducting). When using PFSI dispersions in water‐organic solvent mixture, care must be taken not to poison the Pt catalyst through organic decomposition products, a consequence of the thermal treatment of the electrode‐polymer system bonded with PFSI dispersion. In the present study some procedures for preparing Nafion water dispersion, starting from a Nafion‐117 membrane, are described. The morphological characteristics of the prepared dispersions were compared with Nafion commercial dispersion (NCD). Moreover, membranes with a thickness of 5–20 μm were prepared and characterised, using both the obtained and the NCD dispersions. The obtained data showed that Nafion water dispersion, which can be used to prepare the membrane/electrode system, results in thin membranes that absorb more water than NCD membranes, and have equal and/or higher proton conduction than the NCD.     

Modification of polysulfone ultrafiltration membranes by CO2 plasma treatment

Carbon dioxide plasmas were used to modify hydrophobic polysulfone ultrafiltration membranes to create hydrophilic surfaces throughout the membrane structure. The water contact angle of the upstream side of the membrane (facing the plasma) decreased to zero after treatment and did not change even after several months of aging. The water contact angle of the downstream side decreased with increasing CO₂ plasma treatment time and became zero for treatment times ≥ 1 min (P = 10 W). Functional groups introduced by CO₂ plasma treatment were examined using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). For the treated membranes, the atomic concentration of oxygen increased dramatically and small amounts of nitrogen incorporation were also observed. Membrane performance was tested with water flux measurements as well as protein fouling studies. For treated membranes, the water flux recovery measured after protein fouling was significantly higher than that for control membranes, with nearly 100% recovery after gentle cleaning in water. Moreover, the amount of protein adsorption decreased by over 75% for the treated membranes compared to control membranes. This suggests the protein fouling layer is essentially completely reversible on the CO₂ plasma treated membranes.     

Use of Micellar Solutions as Draw Agents in Forward Osmosis

Recent advances in membrane technologies have enhanced the viability of water treatment strategies that employ semipermeable barriers. Forward osmosis (FO), which exploits the natural osmotic pressure gradient between a “draw” solution and a “feed” solution to produce potable water, offers a low‐energy, low‐cost alternative to more conventional treatment methods. Surfactants, because of their tendencies to aggregate into micelles and to adsorb at interfaces, provide intriguing osmotic pressures and offer exploitable properties by which draw solutions can be regenerated. The effectiveness of surfactant‐based FO using cellulose triacetate membranes has been assessed in terms of water flux and reverse surfactant diffusion using cetylpyridinium chloride, sodium dodecylsulfate, and Triton X‐100. The ratios of water flux to surfactant flux exceeded 600 L mol^?1 for all surfactants studied. Surfactant recoveries of over 99 % were achieved by ultrafiltration using regenerated cellulose membranes.     

Pervaporation of 50 wt % ethanol–water mixtures with poly(1‐trimethylsilyl‐1‐propyne) membranes at high temperatures

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) membranes have been used to separate ethanol–water mixtures by pervaporation. This polyacetylene is known to present high affinity toward ethanol, showing high selectivity and ethanol permeation flux. The performance of this polymer in the separation of alcohol–water solutions has been evaluated over long periods (572 h) at a high temperature (75°C) to examine the deterioration of the transport properties in the separation of 50 wt % ethanol–water solutions. Although PTMSP membranes present good characteristics for the separation of gases and liquid mixtures, their organic selectivity decrease with the operating time because of the relaxation processes of the polymeric chains, which affect the free volume of the polymer, the deterioration being more evident for concentrated solutions. The effects of the operation temperature on the characteristic parameters of pervaporation have also been studied to establish how this variable affects the performance of PTMSP membranes. The selectivity increases slightly with the operation temperature, but the effect of the temperature on the separation factor decreases as membranes are degraded with the operation time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2843–2848, 2007     

Funktionalisierung von Ultrafiltrationsmembranen zur Integration von spezifischen Adsorbereigenschaften

By integrating a water‐soluble polymer, which has the ability to complex heavy metal ions into ultrafiltration membranes, the separation process could be enhanced to enable also filtration of these species. In this work, a membrane and an adsorber polymer were functionalized with complementary reactive groups so that the adsorber polymer could be immobilized in the porous support layer of the ultrafiltration membrane via click reaction. The separation performances and membrane characteristics of the synthesized membranes are comparable to those of conventional UF membranes.     

Purification of Ellagic Acid by UF Membranes

Ellagic acid (2, 3, 7, 8‐tetrahydroxy(1)benzopyrano(5, 4, 3‐cde)(1)benzopyran‐5, 10‐dione) was selected as a model pollutant which is present in the tannic fraction of cork processing wastewater. The ultrafiltration of aqueous ellagic acid solutions through three membranes was studied in tangential UF laboratory equipment. Two of the membranes were polyethersulfone (Biomax10K and Biomax5K, with MWCO of 10000 and 5000 Da, respectively), and the third made of regenerated cellulose (Ultracel5K, with MWCO of 5000 Da). The water hydraulic permeability was evaluated for each membrane. The evolution of the permeate flow rate with processing time was followed, and the influence of the main operating variables (feed flow rate, trans‐membrane pressure and nature of the membranes) on the permeate flux was also established. According to the hypothesis of the film theory, the intrinsic and apparent rejection coefficients, as well as the mass transfer coefficients, were also determined, and the values obtained were discussed as a function of the operating conditions used.     

Proton conductive reinforced poly(ethylene‐co‐styrene) membranes

Polymers with ionic conductivity are useful materials for ion exchange membranes, separators, and electrolytes in electrochemical cells. New ionomers are currently being sought to replace the ionomers, which contain fluorine and are harmful to environment and expensive. A new and promising ionomer is a sulfonated ethylene/styrene copolymer. A nearby alternating copolymer with styrene content of 47 mol % was polymerized with metallocene/MAO catalyst. Membranes were prepared by hot‐pressing copolymer films with a glassfiber tissue. Phenyl rings in the copolymers were sulfonated with chlorosulfonic acid as a sulfonating agent. As the alternating structure of the copolymer, sulfonic groups were evenly distributed along the membranes. The membranes were characterized by determining water uptake, ion exchange capacity, proton conductivity, and mechanical properties. The studies revealed that the sulfonated copolymers have promising properties for proton‐conducting applications. All membranes had good ion exchange capacity, ～ 3.5 meq/g, and proton conductivity, over 50 mS/cm. Due to the high water uptake of the sulfonated copolymer, mechanical properties of the membranes were improved by using the glassfiber tissue as reinforcement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of antifouling ultrafiltration membranes from copolymers of polysulfone and zwitterionic poly(arylene ether sulfone)s

The past few decades have witnessed rapid gains in our demands of antifouling membranes such as water purification membranes and hemodialysis membranes. A variety of methodologies have been proposed for improving the antifouling performance and the hemocompatibility of the membranes. In this study, a series of copolymers (PSF-PESSB) containing polysulfone (PSF) and poly(arylene ether sulfone) bearing pendant zwitterionic sulfobetaine groups (PESSB) were prepared via one-pot polycondensation. Subsequently, the ultrafiltration (UF) membranes were prepared from different zwitterion-containing copolymers. The prepared membranes showed high thermal stability and mechanical properties. Besides, it also displayed attractive antifouling performance and blood compatibility. Compared with the original PSF membrane, the amount of protein absorption on the modified membrane was reduced; the flux recovery ratio and the resistance to blood cells were significantly improved. The results of this work suggest that PSF-PESSB membranes are expected to be applied in blood purification. The introduction of zwitterion-containing polymers to membranes paves ways for developing advanced hemodialysis technologies for crucial process.     

Relationship Between Methanol Permeability and Structure of Different Radiation‐Grafted Membranes

Styrene grafted and sulfonated poly(vinylidene fluoride) and poly(vinylidene fluoride‐co‐hexafluoropropylene) films are candidates as electrolytes in direct methanol fuel cells. Their behaviour in water, 1 and 3 mol dm^–3 aqueous methanol, and pure methanol were studied. According to SAXS results, water and methanol‐water solutions have similar effects on the membranes, i.e., the lamellar period increases and the ionic domains enlarge. Furthermore, differences in the ionic domain structures in pure methanol and water were observed. These structural changes together with dissimilar liquid uptakes in water and in methanol are reflected as changes in the conductivities. An increase in the SAXS intensity and changes in the Bragg distance of the ionic peak were observed in methanol compared to aqueous solutions. This may be related to the hydrophobicity of the CH₃ group on methanol. Dissimilarities in methanol permeability through the radiation‐grafted membrane can be related to structural differences in membranes observed with SAXS. Permeabilities were observed to be lower for the radiation‐grafted membranes compared to Nafion® 115, which compensates for the higher area resistance of the experimental membranes and thus improves their performance in a fuel cell.     

The chlorination and chlorine resistance modification of composite polyamide membrane

Membrane‐based separation technology is one of the most active separation technologies being employed in water treatment. Polyamides (PA) are widely used membrane materials because they exhibit excellent performance, such as high flux with high salt rejection, and enhanced stability against wide range of pH and temperature. Unfortunately, PA membranes exhibit extremely poor resistance to chlorine leading to increased operation costs and decreased membrane lifetime. In this study, we find new ways for prolonging membrane lifetime and reducing the operating costs by investigating the chlorination and modification of PA membranes. Varying concentrations of hypochlorite were used to chlorinate a commercial reverse osmosis membrane (BW‐30, DOW). The results showed that short‐time exposure to high concentrations of hypochlorite could cause more serious problems to membranes than long‐time exposure to low concentrations under the similar total exposure. The performance of the chlorinated membranes was recovered to some extent after treatment with NaOH solution (pH 10), indicating that the alkali treatment could initiate the reversible regeneration of chlorinated membranes. Furthermore, an industrial grade epoxy resin was used to modify the membranes to enhance the chlorine resistance via the reaction between the amide nitrogen and epoxy bond. The successful modifications were confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy. Moreover, the chlorination tests showed that the modifications performed in these experiments enhanced the chlorine resistance of the membranes, especially for the membranes exposed to low concentration of chlorine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41584.     

New chlorine‐resistant polyamide reverse osmosis membrane with hollow fiber configuration

New asymmetric hollow fiber reverse osmosis (RO) membrane was developed from a new chlorine‐resistant copolyamide [4T‐PIP(30)] with a piperazine moiety by a conventional phase‐separation method. The new 4T‐PIP(30) hollow fiber membrane has the same low‐pressure RO performance as cellulose triacetate hollow fiber membrane (FR = 205 L/m² day, Rj = 99.6%) and superior chlorine resistance as well as pH resistance to conventional aramid RO membranes. Structural analysis and viscoelastic study revealed that the new hollow fiber consisted of a top skin, dense layer, and microporous layer, and that it began to decrease its elasticity at 80°C in water, which is possibly related to its good and stable RO performance around room temperature. Several kinds of RO modules were made from the new hollow fiber membranes, for which RO performances were stable for 2 years in chlorinated feed water desalination (the free residual chlorine ranged from 0.l to 1.1 mg/L). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 517–527, 2001     

High flux ultrafiltration membranes based on electrospun nanofibrous PAN scaffolds and chitosan coating

Conventional ultrafiltration (UF) or nanofiltration (NF) filters for water treatments are based on porous membranes, typically manufactured by the phase immersion method. The torturous porosity in these membranes usually results in a relatively low flux rate. In this study, we demonstrated a new type of high flux UF/NF medium based on an electrospun nanofibrous scaffold (e.g. polyacrylonitrile, PAN) coupled with a thin top layer of hydrophilic, water-resistant, but water-permeable coating (e.g. chitosan). Such nanofibrous composite membranes can replace the conventional porous membranes and exhibit a much higher flux rate for water filtration. The interconnected porosity of the non-woven nanofibrous scaffold can be controlled partially by varying the fiber diameter (from about 100 nm to a few micrometers) through the electrospinning processing. The example membrane, containing an electrospun PAN scaffold with an average diameter from 124 to 720 nm and a porosity of about 70%, together with a chitosan top layer having a thickness of about 1 μm, although not yet fully optimized, exhibited a flux rate that is an order magnitude higher than commercial NF membranes in 24 h of operation, while maintaining the same rejection efficiency (>99.9%) for oily waste-water filtration.     

Integration of Ultrafiltration Unit Operations in Biotechnology Process Design

A stepwise process design approach is proposed to model membrane unit operations generally in combination with experimental model parameter determination in laboratory scale, in order to predict the purification performance a priori by simulations for multicomponent mixtures. The development of a rigorous model for an ultrafiltration membrane is described. In conceptual process design, the degree of comprehension of all unit operations integrated have to be almost identical to be able of any consistent process proposal taking equipment‐related fluid‐dynamical and kinetic nonidealities besides thermodynamical feasibility into account. Therefore, a process model, combining the most limiting factors within one mathematical model, is established and various filtrations are carried out with a binary solution for validation. Additionally, a standard laboratory equipment is instituted for logging time‐dependent concentration profiles. The practicability of the proposed procedure is proven in order to design and integrate ultrafiltration membranes into total purification processes.     

Permselectivities of 2,2′‐dimethyl‐4,4′‐bis(aminophenoxyl)biphenyl diphenyl methane–based aromatic polyamide membranes for aqueous alcohol mixtures in pervaporation and evapomeation

The separation of aqueous alcohol mixtures was carried out by use of a series of novel aromatic polyamide membranes. The aromatic polyamides were prepared by the direct polycondensation of 2,2′‐dimethyl‐4,4′‐bis(aminophenoxyl)biphenyl (DBAPB) with various aromatic diacids, such as terephthalic acid (TPAc), 5‐tert‐butylisophthalic acid (TBPAc), and 4,4′‐hexafluoroisopropylidenedibenzoic acid (FDAc). The pervaporation and evapomeation performance of these novel aromatic polyamide membranes for dehydrating aqueous alcohol solution were investigated. The solubility of ethanol in the aromatic polyamide membranes is higher than that of water, but the diffusivity of water through the membrane is higher than that of ethanol. The effect of diffusion selectivity on the membrane separation performances plays an important role in the evapomeation process. Compared with pervaporation, evapomeation effectively increases the permselectivity of water. Moreover, the effect of aromatic diacids on the polymer chain packing density, pervaporation, and evapomeation performance were investigated. It was found that the permeation rate could be increased by introduction of a bulky group into the polymer backbone. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2688–2697, 2003     

Cellulose nanopapers as tight aqueous ultra-filtration membranes

Recently, we have demonstrated the use of wood-derived nanocellulose papers, herein termed nanopapers, for organic solvent nanofiltration applications. In this study, we extend the use of these nanopapers to tight ultrafiltration (UF) membranes. The feasibility of such nanopaper-based UF membranes intended for use in water purification is shown. Four types of nanocelluloses, namely bacterial cellulose, wood-derived nanocellulose, TEMPO-oxidized cellulose nanofibrils and cellulose nanocrystals, were used as raw materials for the production of these nanopaper-based membranes. The resulting nanopapers exhibit a transmembrane permeance in the range of commercially available tight UF membranes with molecular weight cut-offs ranging from 6 to 25 kDa, which depends on the type of nanocellulose used. These molecular weight cut-offs correspond to average pore sizes of a few nanometres. The rejection performance of the nanopapers is on the border of nanofiltration and UF. We demonstrate that the pore size of the nanopapers can be controlled by using different types of nanocellulose fibrils.     

Effects of γ‐aminopropyltriethoxylsilane on morphological characteristics of hybrid nylon‐66‐based membranes before electron beam irradiation

Nylon‐66 is a typical semicrystalline polymer that can be crosslinked using crosslinking agents and electron beam irradiation. Hybrid nylon‐66‐based membranes are more porous but denser compared to the pure nylon‐66 membrane. Besides that, hybrid nylon‐66 membranes exhibit higher water uptake and severe swelling in water. Si/nylon‐66 membranes were prepared by adding γ‐aminopropyltriethoxylsilane (APTEOS). Crosslinked silica in nylon‐66 membranes is confirmed with high gel content and Fourier transform infrared peaks, but XRD results showed that there is a low crystalline degree in these membranes. The thermal stability of hybrid nylon‐66 membranes is also less affected by APTEOS. The crosslinking agent only improves storage modulus in hybrid nylon‐66 membranes. After irradiation, it is learned that APTEOS improves separation performance of nylon‐66 membranes. However, excessive APTEOS causes the ratio of effective thickness over porosity (Δx/A_k) reduces significantly resulting a lower permeability membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of Time in Chemical Cleaning of Ultrafiltration Membranes

Chemical cleaning of ultrafiltration membranes is often considered successful when the flux through a cleaned membrane is much higher than through a pristine one. Here, a novel definition of cleaning intensity is proposed as the product of the concentration of the cleaning agent and the cleaning time (Ct), and it is shown that Ct values between 0.5 and 1.0 g h L^–1 are sufficient for effective cleaning. Experiments with PES‐30 and PVDF‐30 membranes fouled by bovine serum albumin and cleaned with surfactant, oxidant, and formulated cleaning agents demonstrate that a good cleaning should last for 10–20 min and restore the flux through a virgin membrane. More intensive cleaning increases the membrane hydrophilicity and the water flux, but soon causes more severe fouling and even membrane disintegration.     

In‐situ cross‐linked PVDF membranes with enhanced mechanical durability for vacuum membrane distillation

A novel and effective one‐step method has been demonstrated to fabricate cross‐linked polyvinylidene fluoride (PVDF) membranes with better mechanical properties and flux for seawater desalination via vacuum membrane distillation (VMD). This method involves the addition of two functional nonsolvent additives; namely, water and ethylenediamine (EDA), into the polymer casting solution. The former acts as a pore forming agent, while the latter performs as a cross‐linking inducer. The incorporation of water tends to increase membrane flux via increasing porosity and pore size but sacrifices membrane mechanical properties. Conversely, the presence of EDA enhances membrane mechanical properties through in‐situ cross‐linking reaction. Therefore, by synergistically combining the effects of both functional additives, the resultant PVDF membranes have shown good MD performance and mechanical properties simultaneously. The parameters that affect the cross‐link reaction and membrane mechanical properties such as reaction duration and EDA concentration have been systematically studied. The membranes cast from an optimal reaction condition comprising 0.8 wt % EDA and 3‐hour reaction not only shows a 40% enhancement in membrane Young's Modulus compared to the one without EDA but also achieves a good VMD flux of 43.6 L/m²‐h at 60°C. This study may open up a totally new approach to design next‐generation high performance MD membranes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4013–4022, 2016     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008